Abstract

The octanuclear Na2Ni6 complex (Pr3NH)[Na2Ni6(L)4(Bza)5(HBza)(OH)2(ace)]·Et2O (1), where Pr3NH+ = the tripropylamonium cation, H2L = 2-[(E)-(2-hydroxybenzylidene)amino]phenol, HBza = benzoic acid and ace = acetone, was synthesized and characterized by the elemental analysis, FTIR spectroscopy, single crystal X-ray diffraction analysis, magnetic measurements and DFT calculations. All six NiII atoms are hexacoordinate with the {NiO6} or {NiNO5} chromophores forming two defective dicubane cores. The static magnetic data were fitted to the simplified spin Hamiltonian model which resulted in averaged ferromagnetic and antiferromagnetic exchange parameters J = +5.3 cm−1, and J = −9.2 cm−1, respectively, confirming the predominant role of the antiferromagnetic coupling in 1. The broken symmetry DFT method with various functionals (B3LYP, PBE0, TPPSh and CAM-B3LYP) was used to dissect information about magnetic coupling. As a result, the isotropic exchange parameters (Jab) derived by the PBE0 or B3LYP functionals seem to be the best to match the experimental magnetic data.

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